Anti‐inflammatory drugs. IX.

In the solid‐state structure of the title compound, C₄H₁₂N⁺·C₁₄H₁₀Cl₂NO₂^?·H₂O, the asymmetric unit contains one cation, one anion and a water mol­ecule. A complex network of hydrogen bonds is present. A comparison is made with the structure of the an­hydro­us salt.     

Hydro­gen bonding in proton‐transfer compounds of 5‐sulfosalicylic acid with bicyclic heteroaromatic Lewis bases

The crystal structures of quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate trihydrate, C₉H₈N⁺·C₇H₅O₆S⁻·3H₂O, (I), 8‐hydroxy­quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate monohydrate, C₉H₈NO⁺·C₇H₅O₆S⁻·H₂O, (II), 8‐amino­quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate dihydrate, C₉H₉N₂⁺·C₇H₅O₆S⁻·2H₂O, (III), and 2‐carboxy­quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate quinolinium‐2‐carboxylate, C₁₀H₈NO₂⁺·C₇H₅O₆S⁻·C₁₀H₇NO₂, (IV), four proton‐transfer compounds of 5‐sulfosalicylic acid with bicyclic heteroaromatic Lewis bases, reveal in each the presence of variously hydrogen‐bonded polymers. In only one of these compounds, viz. (II), is the protonated quinolinium group involved in a direct primary N⁺—H⋯O(sulfonate) hydrogen‐bonding interaction, while in the other hydrates, viz. (I) and (III), the water mol­ecules participate in the primary intermediate interaction. The quinaldic acid (quinoline‐2‐carboxylic acid) adduct, (IV), exhibits cation–cation and anion–adduct hydrogen bonding but no direct formal heteromolecular interaction other than a number of weak cation–anion and cation–adduct π–π stacking associations. In all other compounds, secondary interactions give rise to network polymer structures.     

Cyclometallated compounds. XV.

The title complex, tetra‐μ‐acetato‐O:O′‐bis{[μ‐1,4‐bis(2‐­pyridyl­oxy)­phenyl­ene‐N,C²:N′,C⁶]dipalladium(II)} bis­(tri­chloro­methane) dihydrate, [Pd₄(C₁₆H₁₀N₂O₂)₂(C₂H₃O₂)₄]·2CHCl₃·2H₂O, the product of the reaction of 1,4‐bis(2‐pyridyl­oxy)­benzene with palladium acetate, is shown to be a tetranuclear, rather than a polymeric, species. It crystallizes about a centre of inversion and has two doubly cyclo­palladated ligands bridged by four acetate groups. The cyclo­palladated ligand is far from planar in the complex and has the central benzene rings π‐stacked. The chelate rings exist in shallow boat conformations.     

Tetrakis(3,5‐di­methyl­pyridine)­dihydrido­silicon dibromide bis(aceto­nitrile) solvate and 3,5‐dimethylpyridinium bromide

In the course of an attempt to synthesize tetrakis(3,5‐di­methyl­pyridine)­dihydridosilicon dibromide, crystals of its aceto­nitrile disolvate, C₂₈H₃₈N₄Si²⁺·2Br^?·2C₂H₃N, (I), and of 3,5‐di­methyl­pyridinium bromide, C₇H₁₀N⁺·Br^?, (II), were obtained in the same reaction flask. They have both been structurally characterized.     

Candibirin A,a furano­coumarin dimer isolated from Heracleum candicans Wall.

Candibirin A [systematic name: 9,9′‐(1,4‐dioxane‐2,5‐diyldi­methyl­ene­dioxy)­di(7H‐furo­[3,2‐g]­chromen‐7‐one)], a new furano­coumarin dimer, was isolated from Heracleum candicans Wall . ¹H NMR and MS spectra had indicated that the title compound was a dimer of heraclenin or heraclenol, but the linkage structure and its chirality were undetermined. The dioxane linkage, having the R,R configuration, has now been elucidated from di­methyl sulfoxide‐solvated crystals, C₃₂H₂₈O₁₀·2C₂H₆OS. Candibirin A is thus a dimerization product from heraclenin formed by reaction at the epoxy group. Di­methyl­form­amide‐solvated crystals, C₃₂H₂₈O₁₀·C₃H₇NO, adopt a different conformation, with a folded structure that differs from the extended structure in the dimethyl sulfoxide solvate. However, the puckering of the dioxane linker unit is very similar in the two conformers. This result shows that the rotation of the ether bonds, in the linker between the furano­coumarin and dioxane moieties, causes the conformational flexibility of (I).     

A structural hierarchy in the hydrogen‐bonded adduct ethane‐1,2‐di­phospho­nic acid–4,4′‐bipyridyl–water (1/1/2): an N‐component N‐­dimensional structure (N = 3) with substructures having N = 1 and 2

The title compound, 4,4′‐bipyridinium ethane‐1,2‐diyl‐1,2‐di­phospho­nate dihydrate, is a hydrated salt, C₁₀H₁₀N₂²⁺·­C₂H₆O₆P₂^2?·2H₂O, in which the components are linked by extensive hydrogen bonding. The cations and anions lie on inversion centres and with the water mol­ecules each form separate one‐component one‐dimensional chains along [100]: the anions and the water mol­ecules form a two‐component two‐dimensional substructure, (001) sheets, while the cations and anions form a second two‐component two‐dimensional substructure, (011) sheets. All three components combine to form a three‐dimensional framework.     

Solid‐state architecture of saccharin salts of some diamines

Hydrazinium saccharinate, N₂H₅⁺·C₇H₄NO₃S⁻, crystallizes in a 1:1 ratio, while ethyl­ene­diaminium bis­(saccharinate), C₂H₁₀N₂²⁺·2C₇H₄NO₃S⁻, and butane‐1,4‐diaminium bis­(sac­charin­ate), C₄H₁₄N₂²⁺·2C₇H₄NO₃S⁻, form in a 1:2 cation–anion stoichiometry. The structures contain many strong hydrogen bonds of the N⁺—H⋯N⁻, N⁺—H⋯O, N—H⋯O and N—H⋯N types, with auxiliary C—H⋯O inter­actions.     

Sodium thio­phenolate N,N,N′,N′-tetra­methyl­ethyl­enedi­amine

The title compound, Na⁺·C₆H₅S⁻·C₆H₁₆N₂, forms lipophilically wrapped infinite sodium chains along the a axis. Each sodium cation is coordinated by three thio­phenolate S atoms and two N centres of one tetra­methyl­ethyl­enedi­amine molecule.     

Hydrogen bonding in two salts of 3‐methylthio‐4‐(propargylthio)quinoline

In 3‐methyl­thio‐4‐(propargyl­thio)­quinolinium chloride monohydrate, C₁₃H₁₂NS₂⁺·Cl^?·H₂O, and 3‐methyl­thio‐4‐(propargyl­thio)­quinolinium tri­chloro­acetate, C₁₃H₁₂­NS₂⁺·­C₂Cl₃O₂^?, the terminal alkyne group forms C[triple‐bond]C—H?O hydrogen bonds of favourable geometry. The conformation of the flexible propargyl­thio group is different in the two structures.     

Hydrogen bonding in the inner-salt zwitterion and in two different charged forms of 5,6-bis(2-pyridyl)pyrazine-2,3-dicarboxylic acid

5,6-Bis(2-pyridyl)­pyrazine-2,3-di­carboxyl­ic acid exists as an inner-salt zwitterion, 3-carboxy-5-(2-pyridinio)-6-(2-pyridyl)­pyrazine-2-carboxyl­ate, (Ia), C₁₆H₁₀N₄O₄. The adjacent pyridine and pyridinium rings are almost coplanar due to the presence of an intramolecular hydrogen bond involving the pyridine N atom and the NH H atom of the pyridinium group. In the crystal of (Ia), symmetry-related mol­ecules are hydrogen bonded via the carboxyl­ic acid OH group and one of the carboxyl­ate O atoms to form a polymer, which exhibits a channel-type structure. In the HCl, HClO₄ and HPF₆ salts, 6-­carboxy-5-carboxyl­ato­pyrazine-2,3-diyldi-2-pyridinium chloride 2.25-hydrate, (II), C₁₆H₁₁N₄O₄⁺·Cl⁻·2.25H₂O, 6-­carboxy-5-carboxyl­ato­pyrazine-2,3-diyldi-2-pyridinium perchlor­ate trihydrate, (IIIa), C₁₆H₁₁N₄O₄⁺·ClO₄⁻·3H₂O, and 6-car­boxy-5-carboxyl­ato­pyrazine-2,3-diyldi-2-pyridinium hexa­fluoro­phosphate trihydrate, (IIIb), C₁₆H₁₁N₄O₄⁺·PF₆⁻·3H₂O, both pyridine rings are protonated. In the perchlorate form, and in the isomorphous hexa­fluoro­phosphate form, the mol­ecule possesses C₂ symmetry, with has a symmetrical intramolecular hydrogen bond involving the adjacent carboxyl­ate and carboxyl­ic acid substituents. In the crystals of the chloride and perchlorate (or hexa­fluoro­phosphate) salts, hydrogen-bonded polymers are formed which are three-dimensional and one-dimensional, respectively.     

Two salts of di‐p‐toluoyltartaric acid with aromatic amines

The structures of bis­[(R)‐(+)‐1‐phenyl­ethyl­ammonium] (2R,3R)‐(−)‐2,3‐di‐p‐toluoyloxybutane­dioate methanol disolvate monohydrate, 2C₈H₁₂N⁺·C₂₀H₁₆O₈²⁻·2CH₄O·H₂O, (I), and bis­(benzyl­ammonium) (2R,3R)‐(−)‐2,3‐di‐p‐toluoyl­oxy­butane­­dioate dihydrate, 2C₇H₁₀N⁺·C₂₀H₁₆O₈²⁻·2H₂O, (II), exhibit extensive hydrogen bonding, with (N—)H⋯O and (O—)H⋯O distances in the ranges 2.716 (2)–2.929 (3) and 2.687 (2)–2.767 (2) Å, respectively, in (I), and 2.673 (2)–2.888 (2) and 2.785 (2)–2.931 (2) Å, respectively, in (II). The amine groups are protonated and the carboxyl­ate groups of the tartrate anions are fully deprotonated. The conformation of the toluoyltartrate anion and its mol­ecular parameters are similar in both structures.     

Two crystals of doubly protonated melaminium salts: melaminium bis­(trifluoro­acetate) trihydrate and melaminium bis­(trichloro­acetate) dihydrate

Crystals of 2,4,6‐triamino‐1,3,5‐triazine‐1,3‐dium bis­(trifluoro­acetate) trihydrate, C₃H₈N₆²⁺·2CF₃COO⁻·3H₂O, and 2,4,6‐triamino‐1,3,5‐triazine‐1,3‐dium bis­(trichloro­acetate) dihydrate, C₃H₈N₆²⁺·2CCl₃COO⁻·2H₂O, both contain doubly protonated melamine rings that lie on crystallographic twofold axes. In the former structure, one water mol­ecule also lies on a twofold axis. While the trifluoro­acetate compound crystallizes in a centrosymmetric space group, the trichloro­acetate is non‐centrosymmetric, so it is useful as a material for non‐linear optics. The efficiency of second harmonic generation is about three times greater than that of KDP (KH₂PO₄). A combination of ionic and donor–acceptor hydrogen‐bond inter­actions link the melaminium(2+) residues with trifluoro­acetate or trichloro­acetate ions and water mol­ecules to form a three‐dimensional network.     

Bis(isoquinoline‐1‐carboxylato‐κ2O,N)(1,10‐phenanthroline‐κ2N,N′)zinc(II) dimethylformamide sesqui­solvate

The asymmetric unit of the title compound, [Zn(C₁₀H₆NO₂)₂(C₁₂H₈N₂)]·1.5C₃H₇NO, contains one monomeric zinc com­plex and 1.5 disordered di­methyl­form­amide solvate mol­ecules. The Zn atom is coordinated to one 1,10‐phenanthroline ligand and to two iso­quinoline­carboxyl­ate anions (IQC^?) via their N and O atoms. The complex exhibits a distorted octahedral geometry around the Zn^II atom, with the apical positions occupied by the O atoms of the IQC^? ligands. The Zn atom lies 0.049 (1) Å out of the basal plane. The crystal packing is characterized by several hydrogen bonds.     

A new trinuclear cobalt(II) complex: deca­aqua-1κ3O,2κ4O,3κ3O-bis­(benzene-1,3,5-tricarboxyl­ato)-1κO,3κO-di-μ-4,4′-bipyridine-1:2κ2N:N′;2:3κ2N:N′-di-4,4′-bipyridine-1κN,3κN-tricobalt(II) 4,4′-bipyridine solvate octa­hydrate

The principal building units in the title compound, [Co₃(C₉H₃O₆)₂(C₁₀H₈N₂)₄(H₂O)₁₀]·C₁₀H₈N₂·8H₂O, are the linear centrosymmetric tricobalt(II) complex mol­ecules resulting from two square-pyramidal [Co(btc)(bpy)(H₂O)₃]⁻ entities (bpy is 4,4′-bipyridine and btc is the benzene-1,3,5-tricarboxyl­ate trianion) bridged by one trans-[Co(bpy)₂(H₂O)₄]²⁺ unit. The trinuclear complex mol­ecules are assembled into infinite chains through inter­molecular O—H⋯N hydrogen bonds and π–π stacking inter­actions between adjacent monodentate bpy ligands. The chains and uncoordinated bpy mol­ecules are further assembled into two-dimensional open layers, which are stacked in a staggered manner to give a three-dimensional supra­molecular architecture with the solvent water mol­ecules in the cavities.     

Hydro­gen bonding in ethyl­ene­di­ammonium bis­(hydrogen malonate) mono­hydrate

In the title compound, C₂H₁₀N₂²⁺·2C₃H₃O₄^?·H₂O, the hydrogen malonate anion has an intramolecular O—H?O hydrogen bond of 2.430 (2) Å. The water mol­ecule lies on a twofold axis and connects the anions into pairs through hydrogen bonds of 2.734 (1) Å. The ethyl­enedi­ammonium cation lies across an inversion centre. Each of the ammonium protons is involved in hydrogen bonding to an anion or a water mol­ecule [N?O 2.815 (2)–2.875 (2) Å].     

1,3‐Propane­di­ammonium bis(3′‐nitro‐trans‐cinnamate) and trans‐1,2‐cyclo­hexane­di­ammonium bis(3′‐nitro‐trans‐cinnamate)

In the title two adducts, C₃H₁₂N₂²⁺·2C₉H₆NO₄^?, (I), and C₆H₁₆N₂²⁺·2C₉H₆NO₄^?, (II), hydrogen bonds between the di­ammonium and carboxyl­ate ions form a two‐dimensional network parallel to the ab plane in (I) and one‐dimensional chains along the c axis in (II). The cyclo­hexane­di­ammonium ion in (II) has a crystallographic twofold axis.     

Cobalt(II) and nickel(II) complexes of quinoline‐2‐carboxyl­ate

The title complexes, trans‐di­aqua­bis­(quinoline‐2‐carboxyl­ato‐κ²N,O)­cobalt(II)–water–methanol (1/2/2), [Co(C₁₀H₆NO₂)₂(H₂O)₂]·2CH₄O·2H₂O, and trans‐di­aqua­bis­(quinoline‐2‐car­box­yl­ato‐κ²N,O)­nickel(II)–water–methanol (1/2/2), [Ni(C₁₀H₆NO₂)₂(H₂O)₂]·2CH₄O·2H₂O, are isomorphous and contain Co^II and Ni^II ions at centers of inversion. Both complexes have the same distorted octahedral coordination geometry, and each metal ion is coordinated by two quinoline N atoms, two carboxyl­ate O atoms and two water O atoms. The quinoline‐2‐carboxyl­ate ligands lie in trans positions with respect to one another, forming the equatorial plane, with the two water ligands occupying the axial positions. The complex mol­ecules are linked together by hydrogen bonding involving a series of ring patterns which include the uncoordinated water and methanol mol­ecules.     

The ternary complex 4‐(2‐pyridyl)pyridinium–3,5‐di­nitro­benzoate–3,5‐di­nitro­benzoic acid (1/1/1)

In the title ternary complex, C₁₀H₉N₂⁺·C₇H₃N₂O₆^?·C₇H₄N₂O₆, the pyridinium cation adopts the role of the donor in an intermolecular N—H?O hydrogen‐bonding interaction with the carboxyl­ate group of the 3,5‐di­nitro­benzoate anion. The mol­ecules of the ternary complex form molecular ribbons perpendicular to the b direction, which are stabilized by one N—H?O, one O—H?O and five C—H?O intermolecular hydrogen bonds. The ribbons are further interconnected by three intermolecular C—H?O hydrogen bonds into a three‐dimensional network.     

4,4′‐(Azino­di­methyl­ene)­dipyridinium chloranilate di­chloro­methane disolvate

The di­chloro­methane disolvate of 4,4′‐(azino­di­methyl­ene)­dipyridinium chloranilate, C₁₂H₁₂N₄²⁺·C₆Cl₂O₄²⁻·2CH₂Cl₂, con­sists of one‐dimensional hydrogen‐bonded molecular tapes that propagate along the [10] direction. Both cations and anions lie across centres of inversion. The molecular tapes are planar but do not stack in the expected segregated manner, instead having chloranilate anions sandwiched between azine groups.